CN104437592A - Alumisilicate molecular sieve catalyst with MWW structure and preparation method of alumisilicate molecular sieve catalyst with MWW structure - Google Patents
Alumisilicate molecular sieve catalyst with MWW structure and preparation method of alumisilicate molecular sieve catalyst with MWW structure Download PDFInfo
- Publication number
- CN104437592A CN104437592A CN201310435163.8A CN201310435163A CN104437592A CN 104437592 A CN104437592 A CN 104437592A CN 201310435163 A CN201310435163 A CN 201310435163A CN 104437592 A CN104437592 A CN 104437592A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- mww structure
- catalyst
- sieve catalyst
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to an alumisilicate molecular sieve catalyst with an MWW structure and a preparation method of the alumisilicate molecular sieve catalyst with the MWW structure. The alumisilicate molecular sieve catalyst with the MWW structure is mainly used for solving the technical problems of relatively high side reaction and insufficient catalyst activity in the existing side-chain aromatic isomerization reaction technology. The problems can be solved very well by adopting a technical scheme that the alumisilicate molecular sieve catalyst with the MWW structure comprises the following components in percentage by weight: a) 10-80% of an alumisilicate molecular sieve with the MWW structure; b) 0.05-3.0% of at least one of VIII-the-family elements or oxides thereof; and c) 19-89% of a binder. The molecular sieve catalyst with the MWW structure can be used for the industrial production of the side-chain aromatic isomerization.
Description
Technical field
The present invention relates to a kind of stratiform Si-Al molecular sieve Catalysts and its preparation method and application of MWW topological structure.
Background technology
Zeolite molecular sieve is that a class is by sharing SiO
2and AlO
2tetrahedron (or other can form tetrahedral respective element) summit and the crystal aluminosilicate (or the crystal of tetrahedron element can be formed containing other) with molecule duct or cage that formed.Be widely used in the field such as synthesis of petroleum refining, petrochemistry, meticulous and specialty chemicals, it has ion-exchange, shape selective catalysis, molecular sieve grade function.
MWW family molecular sieves has identical topological structure, is first succeeded in developing by Mobil company of the U.S. nineties in 20th century and drop into one group of molecular sieve of commercial Application very soon.This family molecular sieves, as important new catalytic material, becomes the focus of catalytic field research and development.Its Major Members comprises PSH-3, SSZ-25, MCM-22 (P), MCM-22 (C), MCM-36, MCM-49, MCM-56, borosilicate zeolite ERB-1, ITQ-1, ITQ-2 equimolecular sieve.The main distinction between different members is that interfloor distance is different with combination degree.Wherein, PSH-3, SSZ-25, MCM-22 (C), borosilicate zeolite ERB-1, ITQ-1 and MCM-49 layer are asked and to be connected with oxo bridge, in conjunction with tight, can not under the effect of swelling agent modification layer spacing: MCM-22 (P) (being called MCM-22 molecular sieve precursor) Coating combination more weak, can modification layer spacing under the effect of swelling agent, therefore, can as the raw material preparing layer column type molecular sieve MCM-36: MCM-56 is then a kind of lamellar zeolite with MWW single layer structure, it is higher that B acid position exposes ratio.ITQ 1 is pure silicon MCM-22; ITQ-1 is a kind of MCM-22 utilizing ultrasonic Separation to obtain.The zeolites catalysis material of three-dimensional structure has stronger acid active sites and selects shape effect, and its channel diameter is generally less than 1 nanometer, cannot hold larger reactant molecule.Compared with three-dimensional structure zeolites catalysis material, mesopore molecular sieve such as MCM-41 etc. has larger aperture, but hole wall is amorphous, acid weak, poor stability.Clay class layered catalytic material has abundant diffusion admittance, but also there is problem that is active and poor stability.MWW molecular sieve has the outer surface B acid position of larger proportion.Topological structure, good stability, better simply synthesis technique and cheaper price that this molecular sieve analog is special. provide possibility for it is applied to more wide field.
MCM-22, MCM-36 and ITQ-2 belong to together and have the layered zeolite molecular sieve that ten-ring and twelve-ring two overlap the MWW topological structure of independent multidimensional pore canal system.Because MWW molecular sieve has the features such as stronger adsorption and desorption ability to large molecule, catalysis hydrocarbon reaction high catalytic activity and stability are shown.
HMCM-22 molecular sieve has independently ten-ring and twelve-ring pore passage structure, and ten binary large apertures are conducive to carbonium ion generation isomerization reaction, and relatively weak acidity also suppresses the carrying out of cracking reaction.Compared with HMCM-22, HITQ-2 and HMCM-36 has larger specific area than its parent, and its supercage that is softened or that break makes reaction molecular easier close to active sites, and isomerization reaction occurs.
Layered zeolite, as the solid acid catalyst material of structure uniqueness, has larger specific area and highly acid outer surface activated centre (suitable with corresponding three-dimensional structure zeolite acidity), shows very excellent absorption and catalytic performance to large molecule.Pass through
optimum synthesis technique, can prepare high-specific surface area have large numberator height can and the lamellar zeolite of outer surface active sites;
through suitable modification, as the active component etc. regulating silica alumina ratio, introducing hetero-atoms, load is applicable to, layered zeolite material can be used as efficient catalyst materials application in corresponding macromolecular reaction.This lamellar zeolite can be used for petrochemical industry, as the synthesis etc. of light materialization of heavy oil, condensed-nuclei aromatics lighting, xylene isomerization, ethylbenzene, isopropylbenzene.
Xylene isomerization is exactly will be PX by catalyst action by meta-xylene and/or ethylbenzene conversion containing the C8 aromatic hydrocarbons mixture of poor PX, thus re-establishing the chemical process of the C8 aromatic hydrocarbons mixture close to dimethylbenzene thermodynamical equilibrium composition, in conjunction with PX separating technology, progressively meta-xylene, ethylbenzene etc. are all converted into PX by cycling, reach the object of volume increase PX.Xylene isomerization determines the economy of Aromatic Hydrocarbon United Plant in aromatics production.
In the Aromatic Hydrocarbon United Plant taking benzene,toluene,xylene as product, the combined unit producing paraxylene occupies critical role.C8 aromatics isomerization unit, as chemical reaction process unique in PX combined unit, directly affects the ruuning situation of this combined unit, and xylene isomerization unit determines the economy of Aromatic Hydrocarbon United Plant in aromatics production.
The domestic and international research to isomerization catalyst at present mainly concentrates on difunctional ethylbenzene conversion type catalyst, improves catalyst activity and selective, thus reduces side reaction, improves dimethylbenzene yield and aromatic hydrocarbons loss, increases economic benefit.(to the selective balance deriving from the hydrogenation/dehydrogenation performance of acidity and metal of pendant alkyl group aromatics isomerization, what more derive from unique pore structure of molecular sieve carrier selects type to isomerization catalyst.By suitably adjusting the acid-metal of catalyst-select type function, the hydrogenation dehydrogenation of catalyst can be improved on the one hand, utilize type of the selecting performance restriction side reaction of molecular sieve on the other hand.）
Conversion of ethylbenzene is the important indicator reflecting C8 arene isomerization catalyst performance quality with being converted into the selective of dimethylbenzene.For ethylbenzene conversion type C8 arene isomerization catalyst, conversion between xylene isomer, only need can be realized by the acid function of catalyst, and ethylbenzene conversion to be the course of reaction of dimethylbenzene very complicated, relate to hydrogenation-isomery-Dehydrogenation Mechanism, need just can complete by bifunctional catalyst, meanwhile, the side reactions such as cracking, disproportionation, de-alkyl also can occur in ethylbenzene conversion process.From the development course of catalyst, the change of metal constituent element is little, and the noble metal component with higher hydrogenation and dehydrogenation activity all selected by nearly all catalyst, and acid constituent element changes greatly.
Current all kinds of C8 arene isomerization catalyst differs from one another, and performance also improves day by day, but for industrial requirements, its activity stability and selective, C8 aromatics yield still Shortcomings.
The present invention is the above-mentioned deficiency overcoming prior art, selects the molecular sieve with MWW structure to be acid constituent element, by effective shape-selection and modification method, has prepared C8 arene isomerization catalyst, in the reaction of C8 aromatics isomerization, shows excellent performance.
Summary of the invention
One of technical problem to be solved by this invention is the technical problem of catalyst activity stability and the selective deficiency existed in prior art, there is provided a kind of silicoaluminophosphate molecular sieve catalyst with MWW structure, this catalyst application has good stability, selective high feature in aromatics isomerization reaction.
Two of technical problem to be solved by this invention is: the preparation method providing the catalyst of one of a kind of technical solution problem.
Three of technical problem to be solved by this invention is poor catalyst stability, the selective low technical problem of the reaction of existing pendant alkyl group aromatics isomerization, provides a kind of method of pendant alkyl group aromatics isomerization.When the method is used for the reaction of pendant alkyl group aromatics isomerization, there is high, the selective high advantage of catalyst stability.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of containing MWW structure silicoaluminophosphate molecular sieve catalyst, in catalyst weight percent, comprises following component:
A) the MWW structure Si-Al molecular sieve of 10 ~ 80%;
B) 0.05 ~ 3.0% group VIII element at least one or its oxide;
C) 19 ~ 89% binding agents.
In technique scheme, in catalyst weight percent, mole silica alumina ratio SiO of described MWW structure lamellar zeolite
2/ Al
2o
3preferable range is 1 ~ 200.The load capacity preferable range of described group VIII element is 0.10 ~ 1.5%.Described group VIII element preferred version is at least one in platinum, palladium, iridium, rhodium element.Wherein a MWW structure lamellar zeolite mole silica alumina ratio preferable range is 15 ~ 100, and its content preferable range is in the catalyst 15 ~ 60wt%; Binding agent preferential oxidation aluminium or boehmite.Preferred technical scheme, in catalyst weight percent, in catalyst also containing 0.1 ~ 5% La, Ce, Pr, Nd rare earth element or its oxide at least one.Preferred technical scheme, in catalyst weight percent, in catalyst also containing 0.01 ~ 5% Cu, Zn, Ca, Mg element or its oxide at least one.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of preparation method containing MWW structural molecule sieve catalyst, comprises following step:
A) the former powder of MWW structure molecular screen sodium form is carried out Fractional Heat-treatment 3 ~ 12 hours, obtain molecular screen primary powder I;
B) described molecular screen primary powder I acid solution of 1 ~ 10% mass concentration is carried out pickling processes 1 ~ 2 hour at 0 ~ 80 DEG C, suction filtration, drying, obtain molecular screen primary powder II;
C) ammonium nitrate solution being 5 ~ 20% by molecular screen primary powder II and mass concentration exchanges, exchange temperature is room temperature ~ 100 DEG C, molecular screen primary powder II is 4 ~ 10 with the solvent and solute weight ratio of ammonium nitrate solution, and swap time is 0.5 ~ 2 hour, obtains molecular screen primary powder III;
D) above-mentioned molecular screen primary powder III is mixed with binding agent, mediate, shaping, obtain catalyst precarsor IV;
E) above-mentioned catalyst precarsor IV is carried out room temperature ageing 0.5-10 hour, 80 ~ 120 DEG C of oven dry, 500 ~ 600 DEG C of roastings 1 ~ 6 hour, obtain catalyst body V;
F) above-mentioned catalyst body V is carried out dipping 12 ~ 24 hours with the modification dipping solution containing group VIII element, then through 70 ~ 110 DEG C of oven dry, 400 ~ 550 DEG C of activation 2 ~ 5 hours, obtain the catalyst containing MWW structure molecular screen.
In technique scheme, heat treatment described in step (a) is in air atmosphere respectively through 150 ~ 200 DEG C, 250 ~ 350 DEG C, 400 ~ 500 DEG C, each 0.5 ~ 3 hour of 550 ~ 600 DEG C of segmentation constant temp. heatings process by the former powder of MWW structure molecular screen sodium form.
Acid solution is selected from least one in salt solution, sulfuric acid, nitric acid, oxalic acid, citric acid, acetic acid, and the weight concentration of acid solution is 5 ~ 10%.
In the present invention, the preparation method of MWW molecular sieve is as follows: first silicon source, aluminium source, template (R), alkali metal chloride and alkali metal hydroxide (M) and water are under agitation obtained initial gel mixture, mixture mole consists of: SiO
2/ Al
2o
3=10 ~ 200; H
2o/SiO
2=5 ~ 500; OH
-/ SiO
2=0.01 ~ 1; M/SiO
2=0.01 ~ 1; R/SiO
2=0.01 ~ 1; Mixture is under 30 ~ 200 DEG C of conditions, and crystallization obtains crystallized product in 1 ~ 400 hour, and this product has the layered zeolite of MWW structure; Described template R is non-equivalence tetraalkylammonium cation, has following general formula:
[
]
+
Wherein R1 is-(CH
2)
mcH
3
R2 is-(CH
2)
ncH
3
r3 is-(CH
2)
lcH
3
r4 is-(CH
2)
kcH
3
Wherein m >=n, and m>l, m>k m is 1,2,3,4
N is 0,1,2,3,4
L is 0,1,2,3
K is 0,1,2,3
M
+for alkali metal cation, take from least one in Li, Na, K, Ru, Cs.
In technique scheme, silicon source is selected from least one in silester, amorphous silica, Ludox, silica gel, diatomite or waterglass; Aluminium source is selected from least one in aluminium hydroxide, aluminium isopropoxide, aluminium secondary butylate, sodium aluminate, aluminum sulfate, aluminum nitrate, aluminium chloride, aluminium oxide; Alkali metal cation M
+/ SiO
2mol ratio be 0.01 ~ 3; Alkali metal cation is taken from the mixture of its chloride and hydroxide, and alkali metal chloride and alkali metal hydroxide mol ratio are 0.02 ~ 50.
Crystallization temperature is 60 ~ 200 DEG C, and crystallization time is 5 ~ 200 hours, and preferred Primogel compound mole consists of SiO
2/ Al
2o
3=2 ~ 100, H
2o/SiO
2=7 ~ 350, OH
-/ SiO
2=0.01 ~ 1, R/SiO
2=0.01 ~ 2, M
+/ SiO
2=0.01 ~ 2.The crystal seed of final MWW structure stratiform weight zeolite 0.02 ~ 10% is added in initial gel mixture before crystallization.
In order to solve the problems of the technologies described above three, the technical solution used in the present invention is as follows: a kind of method of pendant alkyl group aromatics isomerization, take mixed xylenes as raw material, reaction temperature 330 ~ 450 DEG C, reaction pressure 0.1 ~ 1.5MPa, mole hydrogen-hydrocarbon ratio H of mixed xylenes and hydrogen
2/ HC is 0.5 ~ 10, and the mass space velocity of raw material mixed xylenes is 1 ~ 10h
-1condition under, raw material, by the catalyst exposure of beds and any one above-mentioned MWW structure molecular screen, carries out aromatics isomerization reaction.
Catalyst of the present invention uses fixed bed reactors to carry out reactivity worth investigation.Reactor inside diameter φ 25 millimeters, length 1200 millimeters, stainless steel.Adopt electrical heating, temperature automatic control.Reactor bottom filling φ 5 millimeters of beades are as supporter, and filling catalyst 20 grams in reactor, top filling φ 5 millimeters of beades, are made for the use of raw material preheating and vaporization.Mix with hydrogen containing poor paraxylene C8 aroamtic hydrocarbon raw material, pass through beds, isomerization reaction occurs, generate the rudimentary aromatic hydrocarbons such as dimethylbenzene, benzene, and a small amount of more than C9A heavy aromatics and below C4 linear paraffin.
The catalyst that the present invention prepares, the isomerization reaction for the C8 aromatic hydrocarbons mixture comprising ethylbenzene has excellent performance, and above-mentioned fixed-bed micro-devices carries out isomerization reaction performance evaluation to Kaolinite Preparation of Catalyst of the present invention.
Raw material mixed xylenes derives from petrochemical industry Aromatic Hydrocarbon United Plant, and raw material forms: NA 10.4, B 0.02, T0.60, EB 9.57, PX0.34, MX 54.67, OX 24.33,1.3.5 trimethylbenzene 0.01,1.2.4 trimethylbenzene 0.01, other is 0.05 years old.
Symbol description: NA is non-aromatic, B benzene, T toluene, EB ethylbenzene, PX paraxylene, MX meta-xylene, OX ortho-xylene.
Evaluating catalyst condition: 5g catalyst, circulates without hydrogen.
Reaction temperature 330 ~ 450 DEG C, reaction pressure 0.1 ~ 1.5MPa, mole hydrogen-hydrocarbon ratio H
2/ HC=0.5 ~ 10, material quality air speed WHSV=1 ~ 10h
-1.
Catalyst performance index calculates by following formula:
Evaluation index: according to active (the concentration PX/ Σ X of paraxylene in dimethylbenzene and conversion of ethylbenzene C in product
eB) and selective (C8 aronmatic yield Y
c8A) as catalyst performance comparative evaluation index.
Based on constituent mass content relevant calculating formulas and be defined as follows:
ΣX=OX+PX+MX
C
8A=EB+ΣX
PX/ΣX=
×100%
C
EB=
×100%
Y
C8A=
×100%
Below by embodiment, the invention will be further elaborated.
detailed description of the invention
[embodiment 1]
Adopt single modified with noble metals.Taking 300g molecule silica alumina ratio is that the Na type MWW molecular screen primary powder of 30 is in air atmosphere in 200 DEG C, 300 DEG C, 450 DEG C of each roastings 1 hour and 550 DEG C of roastings 3 hours, be that the oxalic acid aqueous solution of 5% is by liquid-solid ratio (quality with mass concentration at 75 DEG C again, lower same) be carry out contact 2 hours under 4 conditions, solid is through suction filtration, washing, under 90 DEG C and liquid-solid ratio are 4 conditions, exchange process is carried out 2 hours with the aqueous ammonium nitrate solution of 10% mass concentration after drying, solid is through suction filtration, washing, dry, repeat 1 ammonium exchange process, namely ammonium type molecular sieve ammonium type MWW molecular sieve is obtained.
Get 100 grams of above-mentioned ammonium type MWW molecular sieves, mix with 150 grams of SB powder, 5 grams of sesbania powder.Add 180ml dilute nitric acid solution (5 % by weight), after abundant kneading on banded extruder extruded moulding, room temperature after drying at 110 DEG C dry 3 hours again, in air atmosphere, 550 DEG C of roastings 3 hours, obtain shaping MWW molecular sieve carrier.
Above-mentioned shaping MWW molecular sieve carrier is shaped to 10 grams, φ 1mm × 1mm particle, flood with platinum acid chloride solution (every 100ml solution is containing Pt 0.37 gram), at room temperature 12 hours are left standstill after stirring, then proceed in baking oven and dry 3 hours through 70 ~ 110 DEG C, again in the lower 500 DEG C of roastings of air atmosphere 3 hours, obtain the catalyst A 1 containing Pt0.3 % by weight.
The catalyst 5 grams getting above-mentioned preparation loads in stainless steel fixed-bed tube reactor, reduce with pure hydrogen, reducing condition: hydrogen flow rate 80ml/min, 2 DEG C/min is warming up to 180 DEG C of constant temperature 2 hours, 375 DEG C are warming up to again with 2.5 DEG C/min, throw raw material mixed xylenes and carry out isomerization reaction, product is analyzed by HP6890 gas-chromatography.Reaction condition: reaction temperature 375 DEG C, reaction pressure 0.6MPa, mixed xylenes weight space velocity is 3.35h
-1, hydrogen/oil mol ratio 3.Online 100 hours reaction results are PX/ Σ X=23.7; C
eB=29.1; Y
c8A=98.3.
[embodiment 2 ~ 8]
Embodiment 2 ~ 8, be respectively by the preparation-obtained catalyst of the present invention of embodiment 1 method, corresponding catalyst sample is labeled as A2 ~ A8, difference is EU-1 silica alumina ratio, it accounts for, and catalyst quality percentage, modified metal mass percentage or kind are different and modification process is different, and concrete preparation condition is in table 1.
Table 1
[embodiment 9 ~ 15]
Embodiment 9 ~ 15 is carry out evaluation response according to embodiment 1 appreciation condition to the preparation-obtained catalyst A 2 ~ A8 of embodiment 2 ~ 8, and within online 100 hours, reaction result is in table 2.
Table 2
| Embodiment | 9/A2 | 10/A3 | 11/A4 | 12/A5 | 13/A6 | 14/A7 | 15/A8 |
| PX/ΣX | 23.59 | 23.50 | 23.63 | 23.51 | 23.69 | 23.25 | 24.06 |
| C E | 31.59 | 30.39 | 29.88 | 29.29 | 30.83 | 30.24 | 29.83 |
| Y C8A | 98.07 | 98.11 | 98.16 | 98.21 | 98.04 | 98.33 | 98.47 |
[embodiment 16]
Adopt two modified with noble metals.
Example 1 gained MWW catalyst carrier particle 10 grams, with H
2ptCl solution (every 100ml solution is containing Pt 0.37 gram) and PdCl
2the mixed solution dipping body of (every 100ml solution is containing Pd 0.5 gram), at room temperature 12 hours are left standstill after stirring, then it is dried 4 hours at 75 ~ 120 DEG C, then 500 DEG C of roastings obtain the present invention couple noble metal catalyst B1 containing 0.3 % by weight Pt and 0.6 % by weight Pd for 3 hours in air atmosphere.Carry out evaluation response according to condition described in embodiment 1 to catalyst B 1, online 100h reaction result is: PX/ Σ X=23.8; C
eB=29.7; Y
c8A=98.5.
[embodiment 17 ~ 26]
Embodiment 17 ~ 26 is respectively according to the preparation-obtained catalyst of the present invention of method described in embodiment 16, corresponding catalyst sample is labeled as B2 ~ B11, it is different that difference is that MWW molecular sieve accounts for catalyst quality percentage, modified metal mass percentage or kind, and concrete preparation condition is in table 3.
Table 3
[embodiment 27 ~ 36]
Embodiment 27 ~ 36 is respectively the preparation-obtained catalyst B 2 ~ B11 of embodiment 17 ~ 26 and carries out evaluation response according to condition described in embodiment 1, and within online 100 hours, reaction result is in table 4.
Table 4
| Embodiment | 27/B2 | 28/B3 | 29/B4 | 30/B5 | 31/B6 | 32/B7 | 33/B8 | 34/B9 | 35/B10 | 36/B11 |
| PX/ΣX | 23.72 | 23.66 | 23.42 | 23.69 | 23.56 | 23.59 | 23.58 | 23.46 | 23.48 | 23.42 |
| C E | 30.47 | 31.45 | 31.96 | 32.49 | 31.01 | 32.12 | 31.52 | 30.37 | 35.81 | 34.87 |
| Y C8A | 98.25 | 98.06 | 97.88 | 97.56 | 98.34 | 97.69 | 98.09 | 97.97 | 97.37 | 97.78 |
Claims (10)
1., containing a silicoaluminophosphate molecular sieve catalyst for MWW structure, in catalyst weight percent, comprise following component:
A) the MWW structure Si-Al molecular sieve of 10 ~ 80%;
B) 0.05 ~ 3.0% group VIII element at least one or its oxide;
C) 19 ~ 89% binding agents.
2. the silicoaluminophosphate molecular sieve catalyst containing MWW structure according to claim 1, is characterized in that mole silica alumina ratio SiO of described MWW structure molecular screen
2/ Al
2o
3be 1 ~ 200; Described group VIII element or the load capacity of its oxide are 0.1 ~ 1.5%.
3. the silicoaluminophosphate molecular sieve catalyst containing MWW structure according to claim 2, is characterized in that mole silica alumina ratio SiO of the Si-Al molecular sieve of described MWW structure
2/ Al
2o
3be 20 ~ 120; Described group VIII element is at least one in platinum, palladium, iridium, rhodium element.
4. the silicoaluminophosphate molecular sieve catalyst containing MWW structure according to claim 2, is characterized in that in catalyst weight percent, in catalyst also containing 0.1 ~ 5% La, Ce, Pr, Nd rare earth element or its oxide at least one.
5. the silicoaluminophosphate molecular sieve catalyst containing MWW structure according to claim 1, is characterized in that in catalyst weight percent, in catalyst also containing 0.01 ~ 5% Cu, Zn, Ca, Mg element or its oxide at least one.
6. the preparation method of the silicoaluminophosphate molecular sieve catalyst containing MWW structure according to claim 1, comprises following step:
A) by the former powder of MWW structure molecular screen of sodium form, carry out Fractional Heat-treatment 0.5 ~ 12 hour, obtain molecular screen primary powder I;
B) described molecular screen primary powder I acid solution of 1 ~ 10% mass concentration is carried out pickling processes 1 ~ 2 hour at 0 ~ 80 DEG C, suction filtration, drying, obtain molecular screen primary powder II;
C) ammonium nitrate solution being 5 ~ 20% by molecular screen primary powder II and mass concentration exchanges, exchange temperature is room temperature ~ 100 DEG C, molecular screen primary powder II is 4 ~ 10 with the solvent and solute weight ratio of ammonium nitrate solution, and swap time is 0.5 ~ 2 hour, obtains molecular screen primary powder III;
D) above-mentioned molecular screen primary powder III is mixed with binding agent, mediate, shaping, obtain catalyst precarsor IV;
E) above-mentioned catalyst precarsor IV is carried out room temperature ageing 0.5-10 hour, 80 ~ 120 DEG C of oven dry, 500 ~ 600 DEG C of roastings 1 ~ 6 hour, obtain catalyst body V;
F) above-mentioned catalyst body V is carried out dipping 12 ~ 24 hours with the modification dipping solution containing group VIII element, then through 70 ~ 110 DEG C of oven dry, 450 ~ 550 DEG C of activation 2 ~ 5 hours, obtain the silicoaluminophosphate molecular sieve catalyst containing MWW structure.
7. the preparation method of the silicoaluminophosphate molecular sieve catalyst containing MWW structure according to claim 6, it is characterized in that, in step (a), described Fractional Heat-treatment is in air atmosphere respectively through 150 ~ 200 DEG C, 250 ~ 350 DEG C, 400 ~ 500 DEG C, each 1 ~ 3 hour of 550 ~ 600 DEG C of segmentation constant temp. heatings process by the former powder of MWW structure molecular screen of sodium form.
8. the preparation method of the silicoaluminophosphate molecular sieve catalyst containing MWW structure according to claim 6, it is characterized in that, the element modified solution of group VIII of the middle employing of step (f) is the aqueous solution of the metal acid of Pt, Pd, Ir, Rh, metal acid-salt, chloride, ammino-complex, carbonyl complex or its mixture.
9. the preparation method of the silicoaluminophosphate molecular sieve catalyst containing MWW structure according to claim 6, it is characterized in that, acid solution is selected from least one in salt solution, sulfuric acid, nitric acid, oxalic acid, citric acid, acetic acid, and the weight concentration of acid solution is 5 ~ 10%.
10. a method for pendant alkyl group aromatics isomerization take mixed xylenes as raw material, reaction temperature 330 ~ 450 DEG C, and reaction pressure 0.1 ~ 1.5MPa, mole hydrogen-hydrocarbon ratio H of mixed xylenes and hydrogen
2/ HC is 0.5 ~ 10, and the mass space velocity of raw material mixed xylenes is 1 ~ 10h
-1condition under, raw material, by any one catalyst exposure in beds and claim 1 ~ 4, carries out aromatics isomerization reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310435163.8A CN104437592B (en) | 2013-09-24 | 2013-09-24 | Silicoaluminophosphate molecular sieve catalyst with MWW structures and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310435163.8A CN104437592B (en) | 2013-09-24 | 2013-09-24 | Silicoaluminophosphate molecular sieve catalyst with MWW structures and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104437592A true CN104437592A (en) | 2015-03-25 |
| CN104437592B CN104437592B (en) | 2017-09-15 |
Family
ID=52884801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310435163.8A Active CN104437592B (en) | 2013-09-24 | 2013-09-24 | Silicoaluminophosphate molecular sieve catalyst with MWW structures and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104437592B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050197515A1 (en) * | 2004-03-03 | 2005-09-08 | Saudi Basic Industries Corporation | Catalyst for aromatization of alkanes, process of making and process of using thereof |
| CN1721069A (en) * | 2004-07-12 | 2006-01-18 | 中国石油化工股份有限公司 | Catalyst for toluene disproportionation and alkyl transfer |
| CN1989089A (en) * | 2004-07-29 | 2007-06-27 | 埃克森美孚化学专利公司 | Xylenes isomerization catalyst system and use thereof |
| CN101003022A (en) * | 2007-01-19 | 2007-07-25 | 北京化工大学 | Method for synthesizing MCM-22 molecular sieve catalyst |
| CN102066292A (en) * | 2008-05-07 | 2011-05-18 | 出光兴产株式会社 | Method for producing compound having adamantane structure |
| CN102596861A (en) * | 2009-09-03 | 2012-07-18 | 巴斯夫欧洲公司 | Process for producing benzene from methane |
-
2013
- 2013-09-24 CN CN201310435163.8A patent/CN104437592B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050197515A1 (en) * | 2004-03-03 | 2005-09-08 | Saudi Basic Industries Corporation | Catalyst for aromatization of alkanes, process of making and process of using thereof |
| CN1721069A (en) * | 2004-07-12 | 2006-01-18 | 中国石油化工股份有限公司 | Catalyst for toluene disproportionation and alkyl transfer |
| CN1989089A (en) * | 2004-07-29 | 2007-06-27 | 埃克森美孚化学专利公司 | Xylenes isomerization catalyst system and use thereof |
| CN101003022A (en) * | 2007-01-19 | 2007-07-25 | 北京化工大学 | Method for synthesizing MCM-22 molecular sieve catalyst |
| CN102066292A (en) * | 2008-05-07 | 2011-05-18 | 出光兴产株式会社 | Method for producing compound having adamantane structure |
| CN102596861A (en) * | 2009-09-03 | 2012-07-18 | 巴斯夫欧洲公司 | Process for producing benzene from methane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104437592B (en) | 2017-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101121144B (en) | Catalyst for aromatics alkyl transferring and dealkylation to synthesis benzene and xylene | |
| CN100998950A (en) | Catalyst used for heavy arene lightenation and alkyl transfer and its preparation method | |
| CN105272803B (en) | The method that toluene is disproportionated transalkylation with heavy aromatics | |
| CN101939101A (en) | Aromatization catalyst comprising prolongated silica and methods of making and using same | |
| CN101898152B (en) | Toluene disproportionation and alkyl transfer catalyst and preparation method thereof | |
| US8927798B2 (en) | Aromatic transformation using UZM-39 aluminosilicate zeolite | |
| CN101966467A (en) | Catalyst for C8 aromatics isomerization reaction technology and preparation method thereof | |
| CN100553777C (en) | The aromatic hydrocarbons transalkylation of high selectivity and dealkylation catalyst | |
| US8618343B1 (en) | Aromatic transalkylation using UZM-39 aluminosilicate zeolite | |
| JP5123810B2 (en) | Aromatic isomerization catalyst | |
| CN100377783C (en) | Modifying catalyst for naphtha processed maferial and method therefor | |
| CN103842318B (en) | The catalyzer transformed for hydrocarbon and method | |
| Al-Khattaf et al. | Catalysis of metal supported zeolites for dealkylation–transalkylation of alkyl-aromatics | |
| CN103372459B (en) | Cyclane hydro-conversion catalyst, preparation method and applications | |
| BR112019007036A2 (en) | alkylaromatic conversion catalyst | |
| CN112619690A (en) | Supported catalyst for preparing propylene by propane dehydrogenation and preparation method and application thereof | |
| CN104549456B (en) | Heavy aromatic lightening catalyst and preparation method thereof | |
| CN103551188B (en) | The preparation of the coated central hole zeolite catalyst of micro-pore zeolite and the application in preparing propylene from methanol reaction thereof | |
| US20140296602A1 (en) | Isomerization process with mtw catalyst | |
| CN1769249B (en) | Method for catalytically isomerizing aromatic compound | |
| CN106925339B (en) | Preparation method for the hierarchical pore molecular sieve catalyst of xylene isomerization reaction in C8 aronmatic | |
| CN103769206B (en) | EUO structural molecule sieve catalysts and preparation method thereof | |
| CN104437592A (en) | Alumisilicate molecular sieve catalyst with MWW structure and preparation method of alumisilicate molecular sieve catalyst with MWW structure | |
| CN101357876A (en) | Method for conveying C<+>9 heavy aromatics to light aromatics | |
| CN103120949B (en) | Methylbenzene methylation catalyst for increasing production of o-xylene and p-xylene and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |